CN104560002B - Shale gas pressure break drag reducer and preparation method thereof - Google Patents
Shale gas pressure break drag reducer and preparation method thereof Download PDFInfo
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- CN104560002B CN104560002B CN201310514393.3A CN201310514393A CN104560002B CN 104560002 B CN104560002 B CN 104560002B CN 201310514393 A CN201310514393 A CN 201310514393A CN 104560002 B CN104560002 B CN 104560002B
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- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 53
- 229920000642 polymer Polymers 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000004094 surface-active agent Substances 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims description 30
- 239000007789 gas Substances 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 21
- 238000010526 radical polymerization reaction Methods 0.000 claims description 18
- 239000003999 initiator Substances 0.000 claims description 16
- -1 alkali metal sulfite Chemical class 0.000 claims description 14
- 229910052783 alkali metal Inorganic materials 0.000 claims description 11
- 150000001450 anions Chemical class 0.000 claims description 8
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 7
- 239000001103 potassium chloride Substances 0.000 claims description 7
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 125000000129 anionic group Chemical group 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- VMSBGXAJJLPWKV-UHFFFAOYSA-N 2-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1C=C VMSBGXAJJLPWKV-UHFFFAOYSA-N 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical group 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 239000007870 radical polymerization initiator Substances 0.000 claims description 2
- 239000012966 redox initiator Substances 0.000 claims description 2
- 230000001960 triggered effect Effects 0.000 claims description 2
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims 1
- DPZFPPWWSNNMPI-UHFFFAOYSA-N [S]C=C Chemical compound [S]C=C DPZFPPWWSNNMPI-UHFFFAOYSA-N 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 150000002500 ions Chemical class 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 19
- 239000007864 aqueous solution Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- 239000003795 chemical substances by application Substances 0.000 description 13
- 150000003926 acrylamides Chemical class 0.000 description 11
- 238000013019 agitation Methods 0.000 description 11
- 239000003292 glue Substances 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000011056 performance test Methods 0.000 description 10
- 238000007873 sieving Methods 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 239000003643 water by type Substances 0.000 description 10
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 9
- 238000007605 air drying Methods 0.000 description 9
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 9
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 9
- 238000010998 test method Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 238000010276 construction Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920002401 polyacrylamide Polymers 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- TUDGMESWIBQVBE-UHFFFAOYSA-N C(C=C)(=O)NC(C[Na])CCCCCCCCCC Chemical compound C(C=C)(=O)NC(C[Na])CCCCCCCCCC TUDGMESWIBQVBE-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000003899 bactericide agent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229920013818 hydroxypropyl guar gum Polymers 0.000 description 2
- 235000013847 iso-butane Nutrition 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 150000003871 sulfonates Chemical class 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N trimethylmethane Natural products CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- TWNIBLMWSKIRAT-RWOPYEJCSA-N (1r,2s,3s,4s,5r)-6,8-dioxabicyclo[3.2.1]octane-2,3,4-triol Chemical compound O1[C@@]2([H])OC[C@]1([H])[C@@H](O)[C@H](O)[C@@H]2O TWNIBLMWSKIRAT-RWOPYEJCSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 1
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000255964 Pieridae Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 150000004976 peroxydisulfates Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to shale gas pressure break drag reducer and preparation method thereof, mainly solves the problems, such as that the drag reducer resistance-reducing yield of prior art is low.The present invention by using shale gas with drag reducer in terms of mass fraction, composition includes 1 part of hydrophobic associated polymer, 0.05~20 part of surfactant, the technical scheme of 5~200 parts of KCl and 500~20000 part of water, preferably resolves the technical problem, available for the drag reducer in shale gas exploitation.
Description
Technical field
The present invention relates to oil and gas exploitation field, more particularly to shale gas fracturing fluid drag reducer and its preparation side
Method.
Background technology
As petroleum resources is increasingly in short supply, energy security problem becomes increasingly conspicuous, and shale gas resource turns into countries in the world energy
Fall over each other the focus of research in source circle.At present, for Chinese shale gas resources exploration still in the starting stage is explored, exploitation protects this
A little resources are the important topics that China's energy industry faces.Shale gas exploitation at present is usually using hydraulic fracturing technology, due to page
Liquid displacement is very big, it is necessary to add a certain amount of drag reducer such as hydroxypropyl guar gum, polyacrylamide in clear water when rock air pressure splits
Amine etc., for reducing frictional resistance of the liquid in pipeline, improve construction effect.But conventional polymer matrix pressure break system due to containing
There are water-insoluble and colloid residue, easily cause shale reservoir grievous injury, fracturing fluid is unfavorable for seam net after being cross-linked to form frozen glue
Formed, and the frictional resistance in pipeline can be increased, therefore restriction is brought to construction equipment.Foreign countries change to shale oil and gas reservoir at present
Make, mainly using smooth aqueous systems.In order to increase dissolubility and dispersive property, it is outer that generally drag reducer, which is fabricated to using mineral oil,
The suspension of phase, the use of mineral oil considerably increase the difficulty for returning discharge opeing processing.Conventional hydroxypropyl guar gum is a kind of gala
Mannosan, easily it is degraded by microorganisms, therefore generally also needs to add a certain amount of bactericide in slippery water.Bactericide makes
With bringing more serious environmental problem, make the processing for returning discharge opeing more complicated.Therefore, it is necessary to develop a kind of environmental protection height
Effect and economic drag reducer, so as to reduce operation pressure, improve construction technology success rate and economic benefit.
It is domestic natural also in starting stage, Southwest Petrol University, petrochina in terms of the development of shale gas drag reducer
Gas limited company, petroleum works Institute for Research and Technology of petrochina Henan Oil Field branch company, petrochina northwest oilfield branch work
Journey Institute for Research and Technology, extend the mechanisms such as oil and all carried out research work in terms of shale gas drag reducer, achieve certain
Progress.
A kind of preparation method of shale gas drag reducer of Publication No. CN102977877A patent report, by normal
The method that function monomer is introduced on the polyacrylamide of rule, improves the anti-shear performance of drag reducer, and resistance-reducing yield can reach
70%；Publication No. CN102516975, CN103045226A and CN103010488A patent all report smooth water type drag reduction
The preparation method of agent, but such drag reducer resistance-reducing yield is all than relatively low.
The content of the invention
A) 1 part of hydrophobic associated polymer；
B) 0.05~20 part of surfactant；
C) 5~200 parts of KCl；
D) 500~20000 parts of water；
The mixture that wherein described hydrophobic associated polymer is represented by following masses part obtains through radical polymerization：
A) 100 parts of acrylamide；
B) 0~60 part of radical polymerization anionic monomer；
C) 0.1~60 part of radical polymerization hydrophobic monomer；
D) 200~2000 parts of water.
In above-mentioned technical proposal, described surfactant preferably is selected from nonionic surface active agent, such as polyoxyethylene nonyl phenyl
Vinethene, OPEO, AEO, or their any mixture；Wherein polyoxyethylene nonyl phenyl
EO construction units number independent preferably 4~30 in vinethene and OPEO；Wherein AEO is used
R5-O-(CH2CH2O) n-H is represented, wherein R5Preferably saturated or unsaturated C12~C18Alkyl, can be straight-chain alkyl,
It can also be branched alkyl；It is preferred that n=4~30.
As preferred technical scheme, the shale gas pressure break drag reducer composition includes：A) 1 part of hydrophobic association polymerization
Thing；B) 5~15 parts of surfactant；C) 50~150 parts of KCl；D) 500~700 parts of water；Wherein described hydrophobic association gathers
The mixture that compound is represented by following masses part obtains through radical polymerization：A) 100 parts of acrylamide；B) 50~60 parts of 2-
Acrylamide-2-methylpro panesulfonic acid；C) 0.5~2 part of formula（I）Shown anion hydrophobic monomer, wherein R1For C8~C12
Alkyl, M is selected from NH4Or any one in alkali metal；Wherein described surfactant is selected from NPE
Or OPEO, EO construction units number are 5~15.
In above-mentioned most preferably technical scheme, more more preferably R1For C10Alkyl.In the above-mentioned technical solutions, surface is lived
Property agent is more preferably OPEO.
To solve the two of above-mentioned technical problem, technical scheme is as follows：One of above-mentioned technical problem technology
The preparation method of shale gas pressure break drag reducer in method, successively including following steps：
(a) water, acrylamide, radical polymerization anionic monomer, the hydrophobic list of radical polymerization are added in polymeric kettle
Body, stir to form solution；
(b) pH value of solution is adjusted to 7~10, is added radical polymerization initiator, is triggered 0.5 in 10~30 DEG C of temperature
~1 hour；
(c) it polymerize 2~8 hours at a temperature of 40~60 DEG C, obtains aqueous gel hydrophobic associated polymer.
(d) dry, obtain the hydrophobic associated polymer of dry state；
(e) the desired amount of hydrophobic associated polymer, surfactant, KCl and water are well mixed, obtain shale air pressure
Split and use drag reducer.
In above-mentioned technical proposal, the radical polymerization anionic monomer preferably is selected from 2- acrylamido -2- methyl-prop sulphurs
At least one of acid, acrylic acid, methacrylic acid, vinylbenzenesulfonic acid, vinyl sulfonic acid.
In above-mentioned technical proposal, the radical polymerization hydrophobic monomer preferably is selected from anion hydrophobic monomer or cation hydrophobic
One kind in monomer；The anion hydrophobic monomer preferably has formula（I）Shown formula；The cation hydrophobic monomer is preferred
With formula（II）Shown formula；R1It is preferred that C4~C16Alkyl, M preferably is selected from NH4Or any one in alkali metal；R3And R4
Independently it preferably is selected from C1~C4Alkyl, R2Preferably C12~C22Alkyl, X is preferably halogen, X more preferably chlorine；
（I）；（II）.
In above-mentioned technical proposal, the radical initiator is preferably redox initiator；The radical initiator
Dosage is preferably to account for the 0.003~0.5% of the total weight of monomer；The radical initiator is preferably by selected from ammonium persulfate or alkali
At least one of metal peroxy disulfate salts oxidant and thio selected from alkali metal sulfite, alkali metal bisulfite or alkali metal
At least one of sulfate reducing agent forms.
To solve the three of above-mentioned technical problem, technical scheme is as follows：Page described in one of above-mentioned technical problem
Rock air pressure splits the application in shale gas exploitation with drag reducer.
Such as the dreg reducer solution huge discharge of the 0.005~0.2wt% is preferably rapidly injected by the method for the application
Bottom, it can effectively reduce the circulation friction pressure in operation.
The concentration expressed in percentage by weight of drag reducer in the present invention, in terms of the polymer content in solution.
The key problem in technology of the present invention is to compound hydrophobic association polyacrylamide and surfactant and KCl, drag reducer of the present invention
Resistance-reducing yield can reach 80% when concentration is 0.005~0.2wt%, not take the hydrophobic association polyacrylamide drag reduction of the compound system
The resistance-reducing yield of agent is less than 75%, achieves preferable technique effect.
Embodiment
【Embodiment 1】
1st, the synthesis of polymer
650g deionized waters are first added in polymeric kettle, add 100g acrylamides（AM）, 54g 2- acrylamidos -2-
Methyl propane sulfonic acid（AMPS）, 1.5g 2- acrylamido dodecyl sodium sulfates（NaAMC12S）, stir to being completely dissolved, use
NaOH regulation pH value is 9, and starts to be passed through high pure nitrogen, and temperature in the kettle is down into 15 DEG C after 30min, then sequentially added
0.1wt% aqueous solution of sodium bisulfite 15.5g and 0. 1wt% persulfate aqueous solution 15.5g continue to lead to as initiator
Sealed after nitrogen 30min.Reaction temperature is gradually increased to 45 DEG C after 1 hour, reaction obtains aqueous gel polymerization after 3 hours
Product, the forced air drying 1.5h under 90 oC is cut after glue, sieving is smashed with pulverizer and obtains the hydrophobic associated polymer of dry state.
2nd, the preparation of drag reducer
In 10L water, 1g hydrophobic associated polymers, 10gOP10 and 100gKCl are added, in mechanical agitation 200rpm speed
The lower stirring of degree 20 minutes, obtains 0.01wt% drag reduction agent solution.
3rd, the performance test of drag reducer
It is other according to SY/T 6376-2008 in addition to drag reduction agent solution flows through 1/2 inch of pipe with 10L/min flows
7.13.1 method carries out resistance-reducing performance evaluation in friction-reducing agent of fracturing fluid room in fracturing fluid general technical specifications.Clear water is loaded more
Function flow circuits instrument, measure clear water pass through stable pressure differential deltap during pipelinep 1；Above-mentioned fracturing fluid is determined after the same method
Friction reducer flows through stable pressure differential deltap during pipelinep 2, by formula（1）Calculate resistance-reducing yield η：
（1）
As a result 1 is seen attached list.
Inventors herein have recognized that dropped when shale gas pressure break of the present invention includes following component with drag reducer composition
Resistance rate is up to more than 80%, has superior technique effect：A) 1 part of hydrophobic associated polymer；B) 5~15 parts of surfactant；
C) 50~150 parts of KCl；D) 500~700 parts of water；Wherein described hydrophobic associated polymer represents mixed by following masses part
Compound obtains through radical polymerization：A) 100 parts of acrylamide；B) 50~60 parts of 2- acrylamide-2-methylpro panesulfonic acids；
C) 0.5~2 part of formula（I）Shown anion hydrophobic monomer, wherein R1For C8~C12Alkyl, M is selected from NH4Or in alkali metal
Any one；Wherein described surfactant is selected from NPE or OPEO, EO structures
Number of unit is 5~15.This also in table 1 embodiment 1 with intuitively finding out in other embodiments and the year-on-year data of comparative example.
【Embodiment 2】
1st, the synthesis of polymer
650g deionized waters are first added in a kettle, add 100g acrylamides（AM）, 60g2- acrylamidos -2-
Methyl propane sulfonic acid（AMPS）, 15g 2- acrylamido dodecyl sodium sulfates（NaAMC12S）, stir to being completely dissolved, use
NaOH regulation pH value is 9, and starts to be passed through high pure nitrogen, and temperature in the kettle is down into 15 DEG C after 30min, then sequentially adds 0.
1wt% aqueous solution of sodium bisulfite 17.5g and 0. the 1wt% g of persulfate aqueous solution 17.5 continue logical nitrogen as initiator
Sealed after gas 30min.Reaction temperature is gradually increased to 45 DEG C after 1 hour, reaction obtains gel polymerizate after 3 hours, cuts
After glue under 90 oC forced air drying 1.5h, smash sieving with pulverizer and obtain hydrophobically associating polymers.
2nd, the preparation of drag reducer
In 10L water, 1g hydrophobic associated polymers, 15gOP15 and 100gKCl are added, in mechanical agitation 200rpm speed
The lower stirring of degree 20 minutes, obtains 0.01wt% drag reduction agent solution.
3rd, the performance test of drag reducer
Method of testing is same as Example 1, as a result sees attached list 1.
【Embodiment 3】
1st, the synthesis of polymer
650g deionized waters are first added in a kettle, add 100g acrylamides（AM）, 55.5g2- acrylamidos ten
Dialkyl sulfonates（NaAMC12S）, stirring is 9 with NaOH regulation pH value to being completely dissolved, and starts to be passed through high pure nitrogen,
Temperature in the kettle is down to 15 DEG C after 30min, then sequentially adds 0.1wt% aqueous solution of sodium bisulfite 15.5g and 0. 1wt%
Persulfate aqueous solution 15.5g as initiator, sealed after continuing logical nitrogen 30min.Reaction temperature is gradually risen after 1 hour
To 45 DEG C, reaction obtains gel polymerizate after 3 hours, cuts after glue the forced air drying 1.5h under 90 oC, is smashed with pulverizer
Sieving obtains hydrophobic associated polymer.
2nd, the preparation of drag reducer
In 10L water, 1g hydrophobically associating polymers, 18gOP20 and 100gKCl are added, in mechanical agitation
Stirred 20 minutes under 200rpm speed, obtain 0.01wt% drag reduction agent solution.
3rd, the performance test of drag reducer
Method of testing is same as Example 1, as a result sees attached list 1.
【Embodiment 4】
1st, the synthesis of polymer
650g deionized waters are first added in a kettle, add 100g acrylamides（AM）, 40g methacrylic acids（MAA）、
12g solution properties（C18DMAA）, stirring is 9 with NaOH regulation pH value, and start to being completely dissolved
It is passed through high pure nitrogen, temperature in the kettle is down to 15 DEG C after 30min, then sequentially adds 0.1wt% aqueous solution of sodium bisulfite
15.2g and 0.1wt% persulfate aqueous solution 15.2g seals as initiator after continuing logical nitrogen 30min.Will after 1 hour
Reaction temperature is gradually increased to 45 DEG C, and reaction obtains gel polymerizate after 3 hours, cuts the forced air drying under 90 oC after glue
1.5h, smash sieving with pulverizer and obtain hydrophobic associated polymer.
2nd, the preparation of drag reducer
In 10L water, 1g hydrophobically associating polymers are added, 10gNP10 and 100gKCl are in mechanical agitation 200rpm
Speed under stir 20 minutes, obtain 0.01wt% drag reduction agent solution.
3rd, the performance test of drag reducer
Method of testing is same as Example 1, as a result sees attached list 1.
【Embodiment 5】
1st, the synthesis of polymer
650g deionized waters are first added in a kettle, add 100g acrylamides（AM）, 30g acrylic acid（AA）, 9g ten
Six alkyl dimethyl allyl ammonium chlorides（C16DMAA）, stirring is 9 with NaOH regulation pH value, and start to be passed through to being completely dissolved
High pure nitrogen, temperature in the kettle is down to 15 DEG C after 30min, then sequentially adds 0.1wt% aqueous solution of sodium bisulfite 13.9g
Persulfate aqueous solution 13.9g with 0.1wt% seals as initiator after continuing logical nitrogen 30min.Will reaction temperature after 1 hour
Degree is gradually increased to 45 DEG C, and reaction obtains gel polymerizate after 3 hours, cuts after glue the forced air drying 1.5h under 90 oC, uses powder
Broken machine smashes sieving and obtains hydrophobic associated polymer.
2nd, the preparation of drag reducer
In 10L water, the speed of 1g hydrophobic associated polymers, 20gNP20 and 100gKCl in mechanical agitation 200rpm is added
Lower stirring 20 minutes, obtains 0.01wt% drag reduction agent solution.
3rd, the performance test of drag reducer
Method of testing is same as Example 1, as a result sees attached list 1.
【Embodiment 6】
1st, the synthesis of polymer
650g deionized waters are first added in a kettle, add 100g acrylamides（AM）, 20g vinylbenzenesulfonic acids
（VBS）, 6g2- acrylamido myristyl sodium sulfonates（NaAMC14S）Stirring is 9 with NaOH regulation pH value to being completely dissolved,
And start to be passed through high pure nitrogen, temperature in the kettle is down to 15 DEG C after 30min, then sequentially adds 0.1wt% sodium hydrogensulfite water
Solution 12.3g and 0.1wt% persulfate aqueous solution 12.3g seal as initiator after continuing logical nitrogen 30min.1 hour
Reaction temperature is gradually increased to 45 DEG C afterwards, reaction obtains gel polymerizate after 3 hours, cuts after glue that air blast is done under 90 oC
Dry 1.5h, smash sieving with pulverizer and obtain hydrophobic associated polymer.
2nd, the preparation of drag reducer
In 10L water, the speed of 1g hydrophobic associated polymers, 10gAEO9 and 100gKCl in mechanical agitation 200rpm is added
Lower stirring 20 minutes, obtains 0.01wt% drag reduction agent solution.
3rd, the performance test of drag reducer
Method of testing is same as Example 1, as a result sees attached list 1.
【Embodiment 7】
1st, the synthesis of polymer
650g deionized waters are first added in a kettle, add 100g acrylamides（AM）, 10g acrylic acid（AA）、3g 2-
The sodium alkyl sulfonate of acrylamido ten（NaAMC10S）, stirring is 9 with NaOH regulation pH value, and start to be passed through height to being completely dissolved
Pure nitrogen gas, temperature in the kettle is down to 15 DEG C after 30min, then sequentially add 0.1wt% aqueous solution of sodium bisulfite 11.3g and
0.1wt% persulfate aqueous solution 11.3g seals as initiator after continuing logical nitrogen 30min.By reaction temperature after 1 hour
It is gradually increased to 45 DEG C, reaction obtains gel polymerizate after 3 hours, the forced air drying 1.5h under 90 oC is cut after glue, with crushing
Machine smashes sieving and obtains hydrophobic associated polymer.
2nd, the preparation of drag reducer
In 10L water, the speed of 1g hydrophobic associated polymers, 10gAEO7 and 100gKCl in mechanical agitation 200rpm is added
Lower stirring 20 minutes, obtains 0.01wt% drag reduction agent solution.
3rd, the performance test of drag reducer
Method of testing is same as Example 1, as a result sees attached list 1.
【Embodiment 8】
1st, the synthesis of polymer
650g deionized waters are first added in a kettle, add 100g acrylamides（AM）, 5g2- acrylamido -2- first
Base propane sulfonic acid（AMPS）, 1g 2- acrylamido octyl sodium sulfonates（NaAMC8S）, stir to being completely dissolved, adjusted with NaOH
PH value is 9, and starts to be passed through high pure nitrogen, and temperature in the kettle is down into 15 DEG C after 30min, then sequentially adds 0.1wt% sulfurous
Sour hydrogen sodium water solution 10.6g and 0.1wt% persulfate aqueous solution 10.6g seal as initiator after continuing logical nitrogen 30min
Mouthful.Reaction temperature is gradually increased to 45 DEG C after 1 hour, reaction obtains gel polymerizate after 3 hours, cuts after glue in 90 oC
Lower forced air drying 1.5h, smash sieving with pulverizer and obtain hydrophobic associated polymer.
2nd, the preparation of drag reducer
In 10L water, 1g hydrophobic associated polymers are added, 5gOP10,5gNP10 and 100gKCl are in mechanical agitation 200rpm
Speed under stir 20 minutes, obtain 0.01wt% drag reduction agent solution.
3rd, the performance test of drag reducer
Method of testing is same as Example 1, as a result sees attached list 1.
【Comparative example 1】
1st, the synthesis of polymer
650g deionized waters are first added in a kettle, add 100g acrylamides（AM）, 55.5g 2- acrylamidos-
2- methyl propane sulfonic acids（AMPS）, stirring is 9 with NaOH regulation pH value, and start to be passed through high pure nitrogen, 30min to being completely dissolved
Temperature in the kettle is down to 15 DEG C afterwards, then sequentially adds 0.1wt% aqueous solution of sodium bisulfite 15.5g and 0.1wt% over cure
Sour aqueous solutions of potassium 15.5g seals as initiator after continuing logical nitrogen 30min.Reaction temperature is gradually increased to 45 after 1 hour
DEG C, reaction obtains gel polymerizate after 3 hours, cuts after glue the forced air drying 1.5h under 90 oC, sieving is smashed with pulverizer
Obtain acrylamide copolymerized polymer.
2nd, the preparation of drag reducer
In 10L water, 1g acrylamides copolymerized polymer and 100gKCl are added, under mechanical agitation 200rpm speed
Stirring 20 minutes, obtains 0.01wt% drag reduction agent solution.
3rd, the performance test of drag reducer
Method of testing is same as Example 1, as a result sees attached list 1.
【Comparative example 2】
1st, the synthesis of polymer
2500g deionized waters are first added in a kettle, add 390g acrylamides（AM）, 210g 2- acrylamidos-
2- methyl propane sulfonic acids（AMPS）, 6g 2- acrylamido dodecyl sodium sulfates（NaAMC12S）, stir to being completely dissolved, use
NaOH regulation pH value is 9, and starts to be passed through high pure nitrogen, and temperature in the kettle is down into 15 DEG C after 30min, then sequentially added
0.2wt% aqueous solution of sodium bisulfite 20g and 0.3wt% persulfate aqueous solution 20g continue logical nitrogen as initiator
Sealed after 30min.Reaction temperature is gradually increased to 45 DEG C after 1 hour, reaction obtains gel polymerizate after 3 hours, cuts glue
The forced air drying 1.5h under 90 oC afterwards, smash sieving with pulverizer and obtain hydrophobic associated polymer.
2nd, the preparation of drag reducer
In 10L water, 1g hydrophobic associated polymers and 10g aliphatic alcohol polyoxyethylene sulfonates are added（n=10）With
100gKCl, stirred 20 minutes under mechanical agitation 200rpm speed, the drag reducer being uniformly dissolved.With mass percent
Meter, hydrophobic associated polymer content are 0.01%.
3rd, the performance test of drag reducer
Method of testing is same as Example 1, as a result sees attached list 1
【Comparative example 3】
The preparation of surfactant drag reducer
In 10L water, 10g OP10 and 100gKCl are added, stirs 20 minutes, obtains under mechanical agitation 200rpm speed
To the drag reducer being uniformly dissolved.
The embodiment of table 1 and comparative example resistance-reducing yield result
Note：NP and OP represents NPE and OPEO respectively, and numerical value below represents knot
The number of EO construction units in structure；AEO represents hexadecanol APEO, and numerical value thereafter represents EO construction units in structure
Number.
Claims (8)
1. shale gas pressure break drag reducer, in terms of mass fraction, composition includes：
A) 1 part of hydrophobic associated polymer；
B) 0.05~20 part of surfactant；
C) 5~200 parts of KCl；
D) 500~20000 parts of water；
The mixture that wherein described hydrophobic associated polymer is represented by following masses part obtains through radical polymerization：
A) 100 parts of acrylamide；
B) 0~60 part of radical polymerization anionic monomer；
C) 0.1~60 part of radical polymerization hydrophobic monomer；
D) 200~2000 parts of water；
Wherein, the one kind of the radical polymerization hydrophobic monomer in anion hydrophobic monomer or cation hydrophobic monomer；Institute
Stating anion hydrophobic monomer has formula shown in formula (I)；Cation hydrophobic monomer has the formula shown in formula (II)；R1It is selected from
C4~C16Alkyl, M is selected from NH4Or any one in alkali metal；R3And R4It is independently selected from C1~C4Alkyl, R2For C12~
C22Alkyl, X is halogen；
The surfactant is nonionic surface active agent, selected from NPE, OPEO,
AEO, or their any mixture；
The radical polymerization anionic monomer be selected from 2- acrylamide-2-methylpro panesulfonic acids, acrylic acid, methacrylic acid,
At least one of vinylbenzenesulfonic acid, vinyl sulfonic acid.
2. the preparation method of the shale gas pressure break drag reducer described in claim 1, comprises the following steps：
(a) water, acrylamide, radical polymerization anionic monomer, radical polymerization hydrophobic monomer, stirring are added in polymeric kettle
It is formed uniformly solution；
(b) pH value of solution is adjusted to 7~10, is added radical polymerization initiator, is triggered 0.5~1 in 10~30 DEG C of temperature
Hour；
(c) it polymerize 2~8 hours at a temperature of 40~60 DEG C, obtains aqueous gel hydrophobic associated polymer；
(d) dry, obtain the hydrophobic associated polymer of dry state；
(e) the desired amount of hydrophobic associated polymer, surfactant, KCl and water are well mixed, obtain shale gas pressure break with subtracting
Resist.
3. the preparation method of the shale gas pressure break drag reducer described in claim 2, it is characterised in that the radical polymerization is cloudy
Ion monomer is selected from 2- acrylamide-2-methylpro panesulfonic acids, acrylic acid, methacrylic acid, vinylbenzenesulfonic acid, vinyl sulphur
At least one of acid.
4. the preparation method of the shale gas pressure break drag reducer described in claim 2, it is characterised in that the radical polymerization is dredged
The one kind of aqueous monomer in anion hydrophobic monomer or cation hydrophobic monomer；The anion hydrophobic monomer has formula (I)
Shown formula；Cation hydrophobic monomer has the formula shown in formula (II)；R1It is C4~C16Alkyl, M is selected from NH4Or alkali gold
Any one in category；R3And R4It is independently selected from C1~C4Alkyl, R2For C12~C22Alkyl, X is halogen；
5. the preparation method of the shale gas pressure break drag reducer described in claim 2, it is characterized in that the radical initiator is
Redox initiator.
6. the preparation method of the shale gas pressure break drag reducer described in claim 2, it is characterized in that the radical initiator is used
Measure to account for the 0.003~0.5% of the total weight of monomer.
7. the preparation method of the shale gas pressure break drag reducer described in claim 2, it is characterized in that the radical initiator by
Selected from least one of ammonium persulfate or alkali metal persulphate oxidant and selected from alkali metal sulfite, alkali metal sulfurous acid
At least one of hydrogen salt or alkali metal thiosulfate reducing agent form.
8. application of the shale gas pressure break drag reducer in shale gas exploitation described in claim 1.
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| CN104892838B (en) * | 2015-06-12 | 2017-06-13 | 中国石油大学(华东) | Cloudy non-both sexes hydrophobic associated copolymer of a kind of heatproof and preparation method thereof |
| CN105238381B (en) * | 2015-08-28 | 2018-08-10 | 胜利油田胜利化工有限责任公司 | A kind of function composite lotion state polymer fracturing fluid and preparation method thereof |
| CN105131179A (en) * | 2015-09-22 | 2015-12-09 | 焦作市宏达力生物化工有限公司 | Special heat-salinity-resistant drag reducer for shale gas fracturing and manufacturing technology thereof |
| CN105131180A (en) * | 2015-09-22 | 2015-12-09 | 焦作市宏达力生物化工有限公司 | Special slickwater resistance reducing agent for shale gas fracturing, and manufacturing technique thereof |
| CN105219372B (en) * | 2015-11-19 | 2018-10-16 | 四川光亚聚合物化工有限公司 | A kind of multi-functional composite fracturing liquid system |
| CN109370557A (en) * | 2018-12-09 | 2019-02-22 | 西南石油大学 | An oxidizing fluid suitable for shale oxidation reformation |
| CN110003877B (en) * | 2019-04-12 | 2021-07-27 | 四川申和新材料科技有限公司 | A kind of anti-high salinity clean and viscous slick water, crosslinking agent, variable viscosity resistance reducing agent and preparation method |
| CN111440606B (en) * | 2020-04-28 | 2022-06-10 | 中国石油集团渤海钻探工程有限公司 | Oil-free phase liquid drag reducer and whole-course slickwater fracturing fluid containing same |
| CN111635749A (en) * | 2020-06-11 | 2020-09-08 | 四川光亚聚合物化工有限公司 | Slick water system with resistance reduction and sand carrying functions and preparation method thereof |
| CN114891494A (en) * | 2022-04-29 | 2022-08-12 | 西安石油大学 | Fracturing fluid for large-displacement fracturing and preparation method thereof |
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